Article coated with composition of polysilicic acid and silyl-fluoroolefin

ABSTRACT

A silyl vinyl ether having the formula   WHEREIN X is an alkylene group of two to 10 carbon atoms, or an alkyleneoxyalkylene group of four to 16 carbon atoms, R is an alkyl group of one to six carbon atoms, y is 0, 1 or 2, and R&#39;&#39; is an alkyl group of 1 to 6 carbon atoms; silyl fluoroolefin polymers made by polymerizing the silyl vinyl ether with fluoroolefins, and, optionally, with other vinyl ethers and/or ethylene and/or propylene and/or fluorine-substituted vinyl ether; compositions containing polysilicic acid and silyl fluoroolefin polymer made by polymerizing the silyl vinyl ether with fluoroolefin, and, optionally, with other vinyl ethers; coating compositions containing a compatible solvent and the polysilicic acid/silyl fluoroolefin polymer composition; articles coated with the silyl-fluoroolefin polymer/polysilicic acid composition and a process for coating them; and polymers made by polymerizing the silyl vinyl ether with formaldehyde or trioxane and, optionally, with alkylene oxides and/or dioxolane and/or alkyl vinyl ethers.

United States Patent [1 1 Hermes ARTICLE COATED WITH COMPOSITION OFPOLYSILICIC ACID AND SILYL-FLUOROOLEFIN [75] Inventor: Matthew EdwardHermes,

Wilmington, Del.

[73] Assignee: E. I. du Pont de Nemours and Company, Wilmington, Del.

[22] Filed: Sept. 29, 1971 [21] Appl. No.: 184,947

Related US. Application Data [62] Division of Ser. No. 32,739, April 28,1970, Pat. No.

[52] US. Cl.1l7/l38.8 F, 117/333), 117/138.8 UA,

[51] Int. Cl..... B32b 27/06, B32b 27/08, B44d 5/00 [58] Field of Search260/4482 B, 448.2 Q, 260/4488 R; ll7/138.8 UA, 138.8 F, 33.3;

1451 Nov. 27, 1973 Primary ExaminerWilliam D. Martin AssistantExaminer-Sadie L. Childs Attorney-Earl L. Handley [57] ABSTRACT A silylvinyl ether having the formula wherein X is an alkylene group of one to10 carbon atoms, or an alkyleneoxyalkylene group of three to 16 carbonatoms, R is an alkyl group of one to six carbon atoms, y is 0, 1 or 2,and R is an alkyl group of l to 6 carbon atoms; silyl fluoroolefinpolymers made by polymerizing the silyl vinyl ether with fluoroolefins,and, optionally, with other vinyl ethers and/or ethylene and/orpropylene and/or fluorine-substituted vinyl ether; compositionscontaining polysilicic acid and silyl fluoroolefin polymer made bypolymerizing the silyl vinyl ether with fluoroolefin, and, optionally,with other vinyl ethers; coating compositions containing a compatiblesolvent and the polysilicic acid/silyl fluoroolefin polymer composition;articles coated with the silyl-fluoroolefin polymer/polysilicic acidcomposition and a process for coating them; and polymers made bypolymerizing the silyl vinyl ether with formaldehyde or trioxane and,optionally, with alkylene oxides and/or dioxolane and/or alkyl vinylethers.

14 Claims, No Drawings ARTICLE COATED WITH COMPOSITION OF POLYSI IJICICACID AND SILYL-FLUOROOLEFIN This is a division of application Ser. No.32,739, filed Apr. 28, 1970, nowU.S. Pat. No. 3,714,214.

BACKGROUND OF THE INVENTION This invention relates to alkoxy silyl alkylcompounds and more particularly to polymers made by polymerizing silylvinyl ethers with fluoroolefins or formaldehyde or trioxane and,optionally, with a thrid monomer.

It is known that coatings for poly(methyl methacrylate) and othermaterials which have good initial hardness, ultraviolet resistance andabrasion resistance can be produced from polysilicic acid and copolymersof fluoroolefin and hydroxyalkyl vinyl ether (U. S. Pat. No. 3,429,845).However, such coatings tend to soften on esposure to atmosphericconditions due to their lack of long term moisture resistance. Acomposition of this type having moisture resistance as well as theultraviolet resistance, abrasion resistance and initial hardness of thepolysilicic acid/fluoroolefin-vinyl ether copolymer composition wouldfill a definite need.

Also sought has been a composition which could act as a crosslinkingsite in elastomeric type polymers such as those described in U. S. Pat.No. 3,051,677, but which is thermally stable and allows the elastomer tobe cured with the use of moisture as opposed to the previously usedcomplex cure systems. Another sought-after composition was one whichcould be polymerized with formaldehyde to form a compound which could beused to coat glass roving to render it easier to handle in manufacturingprocesses, i.e. render it more conducive to chopping at high speed andwhich would not degrade polyoxymethylene when the coated chopped rovingwas incorporated into it.

SUMMARY OF THE INVENTION Now according to the present invention amonomer has now been found which fulfills the above requirements. It isa silyl vinyl ether having the formula:

wherein X is selected from the group consisting of an alkylene groupcontaining one to carbon atoms, and an alkyleneoxy-alkylene groupcontaining three to 16 carbon atoms; R is an alkyl group containing oneto six carbon atoms; y is 0, l or 2; and R is an alkyl group containing1 to 6 carbon atoms.

DESCRIPTIONOF THE PREFERRED EMBODIMENTS This silyl vinyl ether can bepolymerized with fluoroolefins, and optionally with fluoroolefins andother vinyl ethers, to produce polymers which, when mixed withpolysilicic acid, give a coating with the soughtafter moistureresistance, ultraviolet resistance, initial hardness and abrasionresistance. The monomer is useful as the crosslinking site in theelastomeric polymers and can be polymerized'with fonnaldehyde-containingmonomers to form a coating compound for glass rov- Alkyl and alkylene asused throughout includes straight, cyclic and branched alkyl or alkylenegroups. Throughout the specification and claims W is not the chemicalsymbol for tungsten but rather, is as defined, mole percent refers tothe mole percent of monomeric units, and consisting essentially o ismeant as not excluding unspecified conditions or materials which do notprevent the advantages of this invention from being realized; inparticular it is not meant to exclude the additives listed hereafter inthe specification, in the stated proportions.

The silyl vinyl ether polymerizes with fluoroolefin monomers both singlyand in combination with other vinyl ethers to form a polymer whichproduces moisture-resistant, ultraviolet-resistant, initially hard, andabrasion-resistant coating compositions when mixed with polysilicicacid, applied as a coating to a substrate, and cured. The silyl vinylether acts as a crosslinking site when polymerized in small amounts withelastomeric monomers, i.e., fluoroolefin singly or in combination withother vinyl ethers, ethylene, propylene and- /or fluorine-substitutedvinyl ether.

A silyl-fluoroolefin polymer, which utilizes the silyl vinyl ether as acrosslinking site for elastomeric polymers and which is an intermediatefor producing hard coatings when mixed with polysilicic acid, is made bypolymerizing 0.2 to 60 mole percent of the silyl vinyl ether with 40 to99.8 mole percent of a substance consisting essentially of to 40 molepercent of at least one polymerizable fluoroolefin of the formula CZCZZ" wherein Z is F, H or Cl, Z is H, F, or Cl and Z" is H, F, Cl, WorOW, W being lower alkyl or perfluoroalkyl groups, preferably of l to 4carbon atoms, and O to 60 mole percent of a monomer selected from theclass consisting of omega-hydroxy alkyl vinyl ethers of three to 13carbon atoms, alkyl vinyl ethers where the alkyl portion contains one to20 carbon atoms, aryl vinyl ethers where the aryl portion contains sixto 20 carbon atoms, aralkyl vinyl ethers where the aralkyl portioncontains seven to 20 carbon atoms, monoalkyl, monovinyl ethers ofmonoalkylene glycols, monoalky], monovinyl ethers of polyalkyleneglycols, ethylene, propylene, and mixtures thereof.

When the silyl-fluoroolefin polymer is to be mixed with polysilicic acidand used as an abrasion resistant coating, the silyl-fluoroolefinpolymer will normally be made by polymerizing l to 60 mole percent(preferably 8 to 60 mole percent) of the silyl vinyl ether with 40 to 99mole percent (preferably 40 to 92 mole percent) of a substanceconsisting essentially of 100 to 40 mole percent of at least onepolymerizable fluoroolefin of the formula CZ CZ'Z" wherein Z is F, Z isF or Cl and Z" is H, F, Cl, W or OW, W being a lower perfluoroalkylgroup preferably of one to four carbon atoms and 0 to 60 mole percent ofa polymerizable vinyl ether selected from the class consisting ofomega-hydroxy alkyl vinyl ethers of three to 13 carbon atoms, alkylvinyl ethers where the alkyl portion contains one to 20 carbon atoms,aryl vinyl ethers where the aryl portion contains six to 20 carbonatoms, aralkyl vinyl ethers where the aralkyl portion contains seven to20 carbon atoms, monoalkyl, mono-vinyl ethers of monoalkylene glycol,monoalkyl, monovinyl ethers of polyalkylene glycols and mixturesthereof. The above composition will hereinafter be referred to as thesilyl-fluoroolefin coating composition.

When the silyl-fluoroolefin polymer is to function as an elastomerictype material, i.e., the silyl vinyl ether component acts as acrosslinking site, the silylfluoroolefin polymer will normally be madeby polymerizing 0.2 to 10 mole percent, preferably 0.5 to 5 molepercent, of the silyl vinyl ether with 99.8 to 90.0 mole percent,preferably 95 to 99.5 mole percent, of a substance consistingessentially of 100 to 40 mole percent of at least one polymerizablefluoroolefin of the formula CZ CZ'Z", wherein there is at least one F,and wherein Z and Z are F, H or Cl and Z" is H, F, Cl, W or OW, W beinglower alkyl or perfluoroalkyl group, preferably of one to four carbonatoms, and to 60 mole percent of a member selected from the classconsisting of alkyl vinyl ethers where the alkyl portion contains one to20 carbon atoms, ethylene, propylene, and mixtures thereof. Thiscomposition is referred to hereinafter as the silyl-fluoroolefinelastomeric composition.

The silyl vinyl ether also forms a compound when it is polymerized withformaldehyde-type monomers which is a coating for glass roving and whichdoesnt degrade polyoxymethylene when the coated chopped roving isincorporated into the polyoxymethylene. Such a composition is a silylpolymer made by polymerizing 0.l to 25 mole percent (preferred 0.5 tomole percent) of the silyl vinyl ether presented above with 99.9 to 75mole percent (preferred 99.5 to 95 mole percent) of a substanceconsisting essentially of 100 to 85 mole percent (preferred 100-93 molepercent) of a member selected from the class consisting of formaldehydeand trioxane and 0 to mole percent (preferred 0 to 7 mole percent) of amember selected from the class consisting of alkylene oxide, dioxolane,alkyl vinyl ether where the alkyl portion contains one to carbon atomsand mixtures thereof. This composition is referred to hereinafter as thesilyl polymer.

The silyl-fluoroolefin coating composition is usually from 90 to 10percent by weight of a composition formed by mixing the coatingcomposition with 10 to 90 percent by weight polysilicic acid (measuredas SiO This silylfluoroolefin coating/polysilicic acid composition isadapted for use as a coating composition by mixing it with a compatiblesolvent. The resulting mixture is up to 40 percent by weight of thesilylfluoroolefin coating/polysilicic acid composition and the remainderis the compatible solvent. The preferred amount of silyl-fluoroolefincoating/polysilicic acid composition in the mixture containing thesolvent is 5 to l5 percent by weight. Compatible solvent is meant toinclude those solvents or solvent systems in which the silylfluoroolefincoating/polysilicic acid composition is soluble, i.e., forms ahomogeneous solution at room temperature, i.e., around 20C. When theamount of polysilicic acid is described as being measured as SiO this ismeant to refer only to the SiO in the composition from the polysilicicacid and not that from the silyl vinyl ether.

The silyl vinyl ether composition as recited above may have varyingcompositions. The preferred compositions, however, are those in which:

X is

R is ---CH;,;

Y is l; and

The preferred polymerizable fluoroolefins which are polymerized with thevinyl ethers to make the silylfluoroolefin polymer aretetrafluoroethylene, vinylidene, fluoride, trifluoromethyl vinyl ether,methyl trifluorovinylether, chlorotrifluoroethylene,hexafluoropropylene, perfluoromethyl vinyl ether, and perfluoropropylvinyl ether. The W of the substituent group on the polymerizablefluoroolefin can include perfluoroalkyl groups or alkyl groupscontaining one to four carbon atoms; in particular, trifluoromethyl,pentafluoroethyl, heptafluoropropyl, methyl and ethyl. More than onefluoroolefin may be used in the silyl-fluoroolefin polymer. For thesilylfluoroolefin coating composition the preferred fluoroolefins aretetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene,perfluoromethyl vinyl ether, and perfluoropropyl vinyl ether or mixturesthereof with tetrafluoroethylene being the most preferred. For thesilyl-fluoroolefin elastomeric composition the preferred fluoroolefinsare tetrafluoroethylene, vinylidene fluoride, trifluoromethyl vinylether, methyl trifluoro vinyl ether, hexafluoropropylene,perfluoromethyl vinyl ether and combinations thereof with a combinationof vinylidene fluoride, and hexafluoropropylene being the mostpreferred.

The vinyl ethers usable in the silyl-fluoroolefin polymer includeomega-hydroxy alkyl vinyl ethers of three to 13 chain atoms,particularly the aliphatics, especially those with the formula CH CHO(CH),,OH, where n is 2 to 8. Particularly useful vinyl ethers are 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxypropylvinyl ether, S-hydroxypentyl vinyl ether, and 6-hydroxyhexyl vinylether. Other useful vinyl ethers include:

2,3-dihydroxypropyl vinyl ether;

3-hydroxy-2,2-dimethylpropyl vinyl ether;

2-methyl-2-hydroxymethyl-3-hydroxypropyl vinyl ether;

2-ethyl-2-hydroxymethyl-3-hydroxypropyl vinyl ether;

3-(hydroxymethyl)-5-hydroxypentyl vinyl ether;2,2-bis(hydroxymethyl)-3-hydroxypropyl vinyl ether;1-hydroxymethyl-4-vinyloxymethylcyclohexane; and 2-[2-hydroxyethoxy]ethyl vinyl ether. The above vinyl ethers may be used alone or incombination with the above vinyl ethers and the following vinyl ethers,which can also be used alone or in combination:

methyl vinyl ether;

isobutyl vinyl ether;

octadecylvinyl ether;

2-methoxyethyl vinyl ether;

2-[2-methoxyethoxy] ethyl vinyl ether; and

2-[methoxymethoxy] ethyl vinyl ether.

A particularly useful alkyl vinyl ether in the silyl polymer andsilyl-fluoroolefin elastomeric composition is methyl vinyl ether whileparticularly useful vinyl ethers in the silyl-fluoroolefin coatingcomposition are 4- hydroxybutyl vinyl ether and methoxy ethyl vinylether.

The preferred alkylene oxides in the silyl polymer are ethylene andpropylene oxide while formaldehyde is preferred over trioxane.

The proportion of components which are polymerized in making thesilyl-fluoroolefin coating composition normally is about 50 mole percentof the polymerizable fluoroolefin and about 50 mole percent of the silylvinyl ether and any other vinyl ether present, because the fluoroolefinand vinyl ether normally polymerize in a lzl ratio. There does not haveto be any vinyl ether present other than the silyl vinyl ether or therecan be as little as 1 mole percent (relative to the total moles of allcomponents) of the silyl vinyl ether, the balance of the vinyl etherportion of the silylfluoroolefin coating composition being other vinylether. Preferably, however, there is at least 8 mole percent of thesilyl vinyl ether relative to the total moles of all components."Examples of preferred silylfluoroolefin coating compositions are apolymer made by polymerizing a substance of about 50 mole percenttetrafluoroethylene, about 42 mole percent 4- hydroxybutyl vinyl ether,and about 8 mole percent methyldiethoxysilylethyl vinyl ether, and apolymer made by polymerizing a substance of about 50 mole percenttetrafluoroethylene, about 33 mole percent methoxyethyl vinyl ether andabout 17 mole percent 2(methyldiethoxysilyl) ethyl vinyl ether.

Examples of preferred silylfluoroolefin elastomeric compositions arethose made by polymerizing a substance of about 0.8 mole percent2(methyldiethoxysilyl) ethyl vinyl ether or4(2-diethoxymethylsilylethoxy) butyl vinyl ether, about 49.2 molepercent methyl vinyl ether, and about 50 mole percent tetrafluoroethylene. Examples of preferred silyl polymers are those made by polymerizinga substance of 0.1 to to 5 mole percent propylene or ethylene oxide, 0.5to 5 mole percent of the silyl vinyl ether (preferably2(methyldiethoxysilyl) ethyl vinyl ether) and 90 to 99.4 mole percent offormaldehyde and those made by polymerizing a substance of 95 to 99.5mole percent formaldehyde and 0.5 to 5 mole percent of the silyl vinylether.

The composition formed when the silyl-fluoroolefin coating compositionis mixed with polysilicic acid is preferably 60 to 75 weight percentsilyl-fluoroolefin coating composition and 25 to 40 (measured as SiOweight percent polysilicic acid. The silyl-fluoroolefin component(referred to in the claims as the silyl containing composition) may bemixtures of the various silyl-fluoroolet'm coating compositionsdescribed above. It can also be a mixture of one of thesilylfluoroolefin coating compositions described above and a polymerwhich is a copolymer of one or a mixture of the fluoroolefins and'one ora mixture of the various other vinyl ethers enumerated above for the.silylfluoroolefin coating composition. The non-silyl copolymer can beas much as about 80 mole percent of silylfluoroolefin component, butpreferably is less than 50 mole percent. In such a fluoroolefin-vinylether polymer the fluoroolefin component is 40 to 60 mole percent,preferably about 50 mole percent, of the total copolymer, while thevinyl ether component is 60 to 40 mole percent and preferably about 50mole percent of the total copolymer. Exemplary of a silyl-fluoroolefincomponent which is a mixtureis one which is about 80 mole percenttetrafluoroethylene/4-hydroxybutyl vinyl ether copolymer and about molepercent tetrafluoroethylene/2(methyldiethoxysilyl) ethyl vinyl ethercopolymer. The polysilicic acid/silylfluoroolefin coating composition asused hereinafter is meant to include the above described mixtures aswell as the single polymers.

Other additives can be added to the polysilicic acid/-silyl-fluoroolefin coating composition to promote levellyl-fluoroolefincoating composition at from 0.05 to 5 percent by weight of the totalweight of the SiO silylfluoroolefin coating composition and blockcopolymer. One such block copolymer is sold by Union Carbide Corporationas Silicone L-520, and is a polymer of dimethyl siloxane grated withpolyethylene oxide and polypropylene oxide. Other examples of useful(alkali resistant) additives are potassium or sodium thiocyanates orsodium or potassium salts of aromatic or aliphatic carboxylic acids,which have no more than 2 carboxylic acid groups and up to 16 carbonatoms. Such additives are usually used in concentrations of 0.02 to 2percent by weight of the total weight of the SiO and silyl-fluoroolefincoating composition. Cyclic polyethers, e.g. 2,5 ,8, l 5 ,l 8,21-hexaoxatricyclo[20.4.0.O ']hexacosane, the use of which is described inVest, U. S. Patent application Ser. No. 614,915, filed Feb. 9, 1967, andnow U.S. Pat. 3,546,318 are useful as aqueous resistant additives. Suchpolyethers are normally used in concentrations of from 0.01 to 5 percentby weight of the total weight of the SiO and silyl-fluoroolefin coatingcomposition. Other additives such as pigments, catalysts such asalpha,alphaazo-bis-isobutyronitrile may also be added to the polysilicicacid/silyl-fiuoroolefin coating composition.

The polysilicic acid/silyl-fluoroolefin coating composition with orwithout the additives depicted above is used as a coating composition.However, to render it conducive to coating, it is normally dissolved ina compatible solvent. The resulting mixture is usually up to 40 percentby weight of the total mixture of the polysilicic acid (measured asSiOQ/silyl-fluoroolefin coating composition. The relative amounts ofsolvent and polysilicic acid/silyl-fluoroolefin coating composition inthe solution depends on, among other things, how thick the final coatingis to be. The solvent or solvent system used depends on the polymeremployed, substrate onto which the coating is to be put, and otherfactors such as evaporation rate required, etc. The solvent should boilbelow 160C. and preferably, below 125C. and have appreciable vaporpressure at below C. The solvents are polar in nature and should becompatible with the other ingredients of the solutions in a wide rangeof proportions. Preferred solvent systems have at least 50 percent byweight of one to six carbon alkanols, e.g., methanol, ethanol, propanol,butanol, etc., up to 15 percent by weight water, and up to about 40percent by weight of one to three carbon alkanoic acids, e.g., formic,acetic, or propionic. Minor amounts of halogenated (chlorine-and/orfluorine-containing) solvents such as trichloroethylene may be present.For coating poly(methyl methacrylate) at least 10 percent by weightalkanoic acid should be present. Other usable solvents include the lowmolecular weight ketones with up through 7 carbon atoms; for example,methyl ethyl ketone, acetone, and methyl isobutyl ketone; ethers such astetrahydrofuran, 1,4-dioxane, diethylene glycol dimethyl ether, andethylene glycol dimethyl ether; and chloroacetic acid.

The polysilicic acid/silyl-fluoroolefin coating composition in thesolvent is useful in coating substrates. By choice of solvent andcomponent polymers, application conditions and pre-treatments (includingpre-coating) of the substrate, the polysilicic acid/silyl-fluoroolefincoating composition can be caused to adhere to substantially all solidsurfaces, i.e., solid substrates. The

polysilicic acid/silyl-fluoroolefin coating composition of thisinvention is therefore useful for coating on wood, metals, glass, andrelatively dimensionably stable synthetic organic polymeric materials insheet or film form (some of which are transparent) such as acrylicpolymer for example, poly(methyl methacrylate); polyesters (includingobjects having fiber fillers) for example, poly(ethylene terephthalate)and polycarbonate, in particular, poly(diphenylol propane) carbonate andpoly(diethylene glycol bis allyl) carbonate; polyamides; polyimides;cellulosic thermoplastics; butyrates; polyvinyl fluoride;acrylonitrile/butadiene/styrene terpolymer; polyvinyl chloride;polystyrene; polyoxymethylene; etc. Polymeric materials coated with thepolysilicic acid/silyl-fluoroolefin coating compositions are useful inthe fabrication of flat or curved plastic enclosures, such as windows,skylights, Windshields, lenses, etc., particularly for transportationequipment. The coated polymeric materials are particularly useful asophthalmic lenses, i.e., a transparent organic polymeric material in theform of an ophthalmic lens has its usefulness significantly increased bycoating with the polysilicic acid/silyl-fluoroolefin coatingcomposition.

A process for treating such substrates comprises contacting the solidsubstrate with the polysilicic acid/silylfluoroolefin coatingcomposition in compatible solvent. This can be done by dipping,spraying, flow coating or doctoring. The volatile materials are thenremoved from the coating by air drying. Air drying is normally carriedout in an atmosphere which is less than about 50 percent relativehumidity (20 to 40 percent preferred) at about 80F. for up to about 16hours. The coated substrate is then cured by heating the coatedsubstrate at from 75 to 200C. for up to about 24 hours, with the usualtime being 30 to 60 minutes at the high temperatures. The temperature ofcuring is preferred at about 170C, although temperatures above the 200C.limit can be used, depending on the substrate. Curing times andtemperatures depend on the substrate as well as the coating composition.

Articles resulting from the above process, i.e., substrates that arecoated with the polysilicic acid/silylfluoroolefin coating compositionusually have a coating which is 0.5 to 20 microns thick, preferably 3 to8 microns.

The silyl polymer can be prepared, i.e., the polymerization isaccomplished, by reacting the monomers depicted above for the silylpolymer at a temperature of from about 20C. to about lC. in the presenceof a perfluoroalkylstibine catalyst which has the formula in which R isperfluoroalkyl of from one to eight carbon atoms. Normally, theresulting polymer has an inherent viscosity of 0.5 to 2.5 with thepreferred being 1.1 to 2.0.

All inherent viscosities presented in this specification and claims arederived from the expression:

1 inh Int/t /C with measurements being made on an Ostwald- Cannon-Fenskeviscometer. In the above expression:

t efflux time of the solvent alone 1. efflux time of the polymersolution C solution concentration 0.500 gm/IOO ml. un-

less otherwise specified In the measurements, the following solvents andtemperatures are used with the various polymers:

silyl-fluoroolefin elastomeric composition 30/3.5tetrahydrofuran/dimethyl formamide solution 30C.

silyl polymer hexafluoroisopropanol 35C.

The silyl-fluoroolefin elastomeric composition is useful as a caulk,sealant, or high performance or oilresistant elastomer for uses in hose,gaskets, fuel tanks,

etc.

The silyl polymer is useful as a coating for glass roving in that itrenders the roving more conducive to high speed chopping yet does notdegrade polyoxymethylene when the coated chopped roving is incorporatedin In the following examples which illustrate, but do not limit theinvention, all parts and percentages are by weight unless otherwisespecified. Throughout the examples steel wool scratch resistancemeasurements are determined from a log scale from a standard wiping testin which 1 is excellent (no abrasion by No. 0000 steel wool at 25 psi.)and 20 is equivalent to uncoated poly(- methyl methacrylate); 0 haze isthe haze development on wiping under standard conditions with a 1:1slurry of water and air cleaner test dust; the Scotch Brand tape gridtest is accomplished by the following procedure: cutting the finishedsurface through with a sharp edge in a series of parallel lines l/l6inch apart and then with a cutting of a similar series 1/16 inch apartat right angles to the first series such that a crosshatched arearesults, firmly pressing a piece of No. 600 Scotch cellophane tape intocontact with the coated area so as to cover the cross-hatched area, andpulling the tape off as rapidly as possible at a angle to the coatedsurface; modulus strength at percent elongation, permanent set, tensilestrength and ultimate elongation in Examples XI to XIII are determinedby ASTM D 412; compression set is determined by ASTM D-395; carbon andhydrogen analysis is by combustion analysis; fluorine analysis is byWickbold analysis, silicon analysis is by Neutron Activation Analysis;notched Izod by ASTM D-256; and tensile strength and tensile elongationin Example XXII are determined by ASTM D-638.

EXAMPLE I To a solution of 470 g. (7.6 moles) of divinyl ether and 90 g.(0.67 mole) of methyldiethoxy silane was added 0.5 g., 5 percentplatinum on carbon. The solution was stirred 6 days at 25C., filteredand the filtrate distilled to give 378 g. (88 percent recovery) ofunreacted, divinyl ether, boiling point 2932C.

Distillation of the residue through an 18-inch spinning band columnresulted in 93 g. (68 percent) of 2(methyldiethoxysilyl) ethyl vinylether, boiling point 4546C. at 1.5 mm Hg. and 7.5 g. of the diadduct ofthe silane to the divinyl ether, boiling point 100104C. at 1 mm Hg. Thestructures were verified by elemental analysis, gas chromatography andinfrared and Nuclear Magnetic Resonance spectroscopy.

EXAMPLE II To a tube was added 1 Kg. methyldiethoxy silane, 5.05 Kg.divinyl ether, and 2.5 g., 5 percent platinum on carbon. The tube wassealed and heated at 100C.

for 4 hours in an autoclave. The result was 1.1 Kg. of'2(methyldiethoxysilyl) ethyl vinyl ether with a boiling point of 4446C.at 1.2 mm Hg.

EXAMPLE 111 To a solution of 710 g. (5.0 moles) of butane diol divinylether and 67 g. (0.50 mole) of methyldiethoxysilane was added 0.5 g. ofpercent platinum on carbon. The reaction mixture was heated at 100C. for4 hours, cooled and filtered to remove the catalyst. On distillation 575g. (90 percent) of the unreacted divinyl ether was recovered, boilingpoint 47-52C. at 5 mm Hg. and 117. g. (85 percent) ofmethyldiethoxysilylethoxybutyl vinyl ether, boiling point 91 to 92C. at0.6 mm Hg. The material was shown to be a single compound by gaschromatography and the structure indicated by elemental analysis andNuclear Magnetic Resonance spectroscopy.

EXAMPLE IV To a solution Of-790 g. 5.0 moles) of divinyl diethyleneglycol and 67 g. (0.5 mole) methyl diethoxysilane was added 0.5 g., 5percent platinum catalyst on car bon. The reaction mixture was heated at100C. for 4 hours. Filtration followed by distillation resulted in 620g. recovered divinyl diethylene glycol, boiling point 47 to 52C. at 1mm. Hg, and 109 g. of methyldiethoxysilylethoxyethoxyethyl vinyl ether,boiling point 100 to 104C. at 0.5 mm Hg. Structural identification wasdetermined by gas chromatography, Nuclear Magnetic Resonancespectroscopy and elemental analysis.

EXAMPLE v A solution of 20.4 g. (0.10 mole) of 2(methyldiethoxysilyl)ethyl vinyl ether (prepared by the procedure described in Example I) in250 ml. (200 g.) of tert-butanol was catalyzed with 0.05 g.alpha,alpha'azobis-isobutyronitrile. The catalyzed solution was placedin a 350 ml. stainless steel pressure tube to which gottetrafluoroethylene was then added. After heating at 70C. for 5 hours,215 g. of viscous, colorless solution was obtained containing 12.4percent by weight tetrafluoroethylene/2(methyldiethoxysilyl) ethyl vinylether copolymer which was essentially 50 mole percent of each.lodometric titration showed that 3.2 percent of the2(methyldiethoxysilyl) ethyl vinyl ether remained unreacted.

EXAMPLE'VI A solution of 14.5 g. (0.125 mole) of 4-hydroxybutyl vinylether, 5.0 g. (0.025 mole) of 2(methyldiethoxysilyl) ethyl vinyl ether,0.05 g. alpha,alpha'azo-bisisobutyronitrile and 250 ml. (200 g.) oftert-butanol was sealed in. a 350 ml. pressure tube. Thirty grams oftetrafluoroethylene was pressurized into the tube and the tube wassealed. The tube was heated at 70C. for 5 hours. The resulting viscoussolution contained 15.5 percent by weighttetrafluoroethylene/4-hydroxybutyl vinylether/2(methyldiethoxysilyl)ethyl vinyl ether terpolymer and showed noresidual vinyl ether. The polymer was 50 mole percenttetrafluoroethylene and the other 50 mole percent was the two vinylethers. The solution was diluted to 11 percent solids with n-butanol.

EXAMPLE VII A solution of 10.2 g. 2(methyldiethoxysilyl)ethyl vinylether, 10.2 g. methoxyethyl vinyl ether and 0.05

g. alpha,alpha'azo-bis-isobutyronitrile inv 250 ml. of tbutanol in a 400ml. stainless steel tube was pressurized to 200 psi. withtetrafluoroethylene and heated 5 hours at 65C. The resulting solution190 g.) contained 14.9 percent tetrafluoro-ethylene/methoxyethylvinylether/- 2(methyldiethoxysilyl)ethyl vinyl ether terpolymer with thetetrafluoroethylene being 50 mole percent of the terpolymer. Thesolution was diluted with 62 g. of methyl ethyl ketone.

EXAMPLE Vlll In this and the following examples the polysilicic acid wasprepared by adding 45 g. of 0. 1N HCl to a solution of 100 g. ethylortho silicate and 47 g. ethanol. The solution which contains 15 percentsilica as SiO was aged 16-64 hours at 25C. before use.

A coating solution was prepared by mixing together at room conditionsthe following ingredients in their respective amounts:

polysilicic acid (amount measured as SiO although in the 15 percentsolution as described above) 25 g.

tetrafluoroethylene/2( methyldiethoxy-silyl) ethyl vinyl ether copolymer(in 12.4 percent solution as described in Example V) 100 g.

acetic acid 40 g.

n-butanol 25 g.

potassium thiocyanate (20 percent solution in methanol) 025 cc.

Silicone L-520 (3 drops) 0.07 g.

Four inch X four inch X one-quarter inch Plexiglas G. cast acrylicpanels (manufactured by Rohm & Haas Corp.) were cleaned in isopropylalcohol, immersed in the coating solution above, soaked in the solutionfor 2 minutes and withdrawn at a rate to give a 2.4 micron thickcoating. The coated panels were air dried at 18 percent relativehumidity at F. for 30 minutes and then cured in a circulating air overfor 1 hour at 170C. The resulting coatings were hard and adherent. Thefollowing table gives the results of exposure of the coatings to percentrelative humidity at 25C. for various time periods.

Steel Wool Time (days) A Haze Scratch Resistance 0 0.3 1 2l 0.3 l 0.9 5

The coatings were exposed to a carbon arc Weather- O-Meter (ASTM-E42-57)and failed in 2000 hours.

EXAMPLE 1X A coating solution was prepared by mixing at room SiliconeL-520 (4 drops) 0.09 g.

Using the procedure of Example VIII acrylic panels were coated withcoatings 3.7 microns thick. These were air-dried at 100 percent relativehumidity at 82F. for 30 minutes and cured for 1 hour at 170C. Thecoatings had good initial hardness, hot water resistance and baseresistance. The following Table shows the Haze and steel wool scratchresistance test results for these coatings at 100% relative humidity and25C. for

various time periods.

Steel Wool Time (days) A Haze Scratch Resistance 0 0.1 1 7 0.7 1 14 1.2l 21 2.3 4 60 4.7 14-20 The coatings did not fail in 2500 hours ofWeather- O-Meter (ASTM-E-42-57) exposure.

EXAMPLE X A coating was prepared by mixingat room temperature theingredients below in their respective amounts:

polysilicic acid (measured as SiO although in a 15 percent solution asdescribed in Example VIII) 27 g. tetrafluoroethylene/methoxyethyl vinylether/2(methyldiethoxysilyl) ethyl vinyl ether terpolymer (in 11 percentsolution as described in Example VII) 94 g. acetic acid 30 g. potassiumthiocyanate percent in methanol) H 0.27 cc. Silicone L-520 0.089 g.

Acrylic panels were coated as in Example VIII with the coating solution.The coatings were dried at 18 percent relative humidity at 80F. for 30minutes and cured for 60 minutes at 170C. Exposure to air at 100%relative humidity at C. yielded the following test results:

Steel Wool Time (days) A Haze Scratch Resistance 0 1.5

EXAMPLE XI A 400 ml. stainless steel bomb was loaded with 0.2 g.alpha,alpha-azobisisobutyronitrile, 6 g. 4(2-ethoxydimethylsilylethoxy)butyl vinyl ether, 120 g. neopentane, 22 g.methyl vinyl ether and 40 g. tetrafluoroethylene, and heated at 70C. for12 hours. After cooling, and drying of the resulting product in a vacuumoven at 60C., 48 g. of a rubbery polymer were obtained.

Anal. Found: C, 39.3%; H, 5.1%; F, 46.6%; and Si 1.27% A mixture of 22.3g. of the above polymer and 4.5 g.

of Easy Process Channel carbon black (containing EXAMPLE XII Into a 400ml. stainless steel bomb was loaded 0.2 g.alpha,alphaazobisisobutyronitrile, 0.7 g. 2(methyldiethoxysilyl) ethylvinyl ether, 120 g. neopentane, 23 g. methyl vinyl ether and 40 g.tetrafluoroethylene, and then the bomb was heated to C. for 12 hours.The resulting polymer was dried under vacuum at 50C. The inherentviscosity of the 52 g. of polymer obtained was 0.77 (solutionconcentration 0.1 percent by weight).

A mixture of 27 g. of the above polymer and 5.4 g. of Easy ProcessChannel carbon black (containing about 15 wt. percent adsorbed water)was milled and then cured in a press for 1 hour at C. and then 2 hoursat 150C. The resulting vulcanizate was insoluble in tetrahydrofuran andhad the following physical properties:

modulus at elongation 220 psi.

tensile strength 730 psi.

ultimate elongation 71.0%

permanent set 1 14% EXAMPLE XIII When a polymerization was run under thesame conditions as Example XII except 1.3 g. of the silyl monomer wasused, and the curing was carried out in the same manner, a vulcanizatewith the following properties was obtained:

modulus at 100% elongation 390 psi.

ultimate elongation 220 tensile strength 1340 psi.

permanent set 10% EXAMPLE XIV Into a 400 ml. stainless steel bomb wascharged with 200 ml. 1,1,2-trichlorotrifluoroethane, 0.2 g.alpha,alpha'-azobis(alpha,aIpha-dimethyl-valeronitrile), 7 g. 4(-2-diethoxymethylsilylethoxy)butyl vinyl ether, 22 g. methyl vinyl etherand 40 g. tetrafluoroethylene. The bomb was heated at 60C. for 10 hours,and then the solvent was removed from the resulting solution undervacuum yielding 47 g. of a grease-like polymer.

EXAMPLE XV A 400 ml. stainless steel bomb was loaded with 60 ml. ethylacetate, 1.6 ml. t-butyl peroxide, 10 g. 4(2-diethoxymethylsilylethoxy)butyl vinyl ether, 45 g. hexafluoropropylene,61 g. vinylidene fluoride and 18 g. tetrafluoroethylene, and sealed.After being heated at for 8 hours the resulting solution was removed,and the volatiles stripped under vacuum at about 60C. The yield ofpolymer was 65.5 g. and it had the following properties:

Anal. Found: C, 35.0%; H, 2.9%; F 61.9% inherent viscosity 0.05(solution concentration 0.2 percent by weight) EXAMPLE XVI Formaldehydewas generated by pyrolysis of cyclohexyl hemiformal at C. The productvapors were directed through a condenser maintained at 16C., thenthrough one U tube approximately one inch in diameter by twelve inchesin height containing a small amount of mineral oil at 25C. at the bottomof the tube which acts as a bubble flow indicator. The formaldehyde wasthen directed into thirteen additional U tubes packed with stainlesssteel. The first U tube was at 25C. and the remainingtwelve were at C.The U tubes removed water, formic acid, and cyclohexanol.

The purified formaldehyde vapor was-passed at a rate of about 1.1parts/min. into a reactor containing 264 parts of benzene, one part of2(methyldiethoxysilyl) ethyl vinyl ether, and 0:09 part of (CF Sb. Thepolymerization proceeded smoothly aftr a 3-minute induction period.After 8 and 14 minutes additional one part amounts of2(methyl-diethoxysilyl) ethyl vinyl ether were added to the reactionmixture which was maintained at 40C. Formaldehyde addition was continuedfor a total of 19 minutes. The reaction was then stirred under nitrogenfor four minutes and quenched with 4 parts of triethylamine in 16 partsof methanol. The crude product was recovered by filtration, washed withthree 250-part portions of acetonerand dried in a vacuum oven at 25C. toyield 24.2 parts of product. The product had an inherent viscosity of1.36.

The crude product was stabilized by solution ester capping. Three partsof crude product was mixed with 54 parts of propionic anhydride and 6parts of quinoline and stirred under nitrogen for 30 min. The polymerwas then taken into solution at 168C. and cooled. The

precipitated polymer was collected by filtration and EXAMPLE xvnFormaldehyde was generated as in Example XVI. The purified formaldehydewas passed at a rateof about 1.1 parts/min. into a reactor containing264 parts of benzene, one part of 2(methyldiethoxysilyl) ethyl vinylether, and 0.09 part of (CF Sb. The polymerization proceeded smoothlyafter a 6-minute induction period. After minutes an additional k part of2(methyldiethoxysilyl)ethyl vinyl ether was added to the reactionmixture which was maintained at 40C. Formaldehyde addition was continuedfor a total of 19 minutes. The reaction mixture was then stirred undernitrogen for three minutes and quenched with 4 parts of triethylamine in16 parts of methanol. The crude product was recovered by filtration,washed with three 250-part portions of acetone and dried in a vacuumoven at C. to yield'22.2 parts of product. Its inherent viscosity was1.63.

The crude product was stabilized by solution ester capping. Three gramsof crude product were mixed with 54 parts of propionic anhydride,'and 6parts of quinoline and stirred under nitrogen for minutes. The polymerwas then taken into solution at 168C. and cooled. The precipitatedpolymer was collected by filtration and washed with three portions of75% acetone 25% methanol followed by two portions of acetone. Theproduct was quantitatively recovered after vacuum drying overnight. Theproduct had a melting point of 170C. as determined by differentialthermal analysis. It was determined by Nuclear Magnetic Resonancemeasurements that the main chains of the copolymer contained 0.5 mole ofthe 2(methyldiethoxysilyl) ethyl vinyl ether.

EXAMPLE XVIII Formaldehyde was generated by pyrolysis ofcyclohexylhemiformal at 145C. The product vapors were directed through acondenser maintained at 16C., then through one U tube approximately oneinch in diameter by twelve inches in height containing a small amount ofmineral oil at 25C. at thebottom of the tube which acts as a bubble flowindicator. The formaldehyde was then directed into thirteen additional Utraps packed with stainless steel. The first U tube was at 25C. and theremaining twelve were at 0C. The U tubes removed water, formic acid, andcyclohexanol.

The purified formaldehyde vapor as passed at a rate of about 1.1parts/minute into a reactor containing 264 parts of benzene, two partsof 2(methyldiethoxysilyl) ethyl vinyl ether, and 4 parts of ethyleneoxide. After approximately 2 minutes, 0.1 part oftris(trifluoromethyl)stibine in 8.6 parts of benzene was added to thereaction mixture which was maintained at 40C. Ethylene oxide wasintroduced into the formaldehyde entering the reactor at a rate of 0.1part/min. Additional onepart amounts of 2(methyldiethoxysilyl) ethylvinyl ether were added at 8 and 14 minutes into the run. Formaldehydeaddition was continued for a total of '19 minutes. The reaction was thenstirred under nitrogen for four minutes and quenched with 4 parts oftriethylamine in 16 parts of methanol. The crude product was recoveredby filtration, washed with three 250-part portions of acetone and driedin a vacuum oven at 25C. to yield 20 parts of product. The product hadan inherent viscosity of 1.4.

The crude product was stabilized by solution ester capping. Three gramsof crude product was mixed with 54 parts of propionic anhydride and 6parts of quinoline and stirred under nitrogen for 30 minutes. Thepolymer was then taken into solution at 168C. and cooled. Theprecipitated polymer was collected by filtration and washed with threeportions of acetone- 25% methanol followed by two portions of acetone.The product was quantitatively recovered after vacuum drying for 16hours at 65C. The product had a melting point of 162C. as determined bydifferential thermal analysis. It was determined by Nuclear MagneticResonance and chemical analysis that approximately 1.0 mole percent ofthe vinyl ether and 0.6 mole percent ethylene oxide had beenincorporated into the main chains of the terpolymer.

EXAMPLE XIX a 3.1 micron thick coating resulted. The coated lenses wereair dried at 50% relative humidity (25C.) for 16 hours, then cured in acirculating air oven for 24 hours at C. The resulting coatings were hard(steel wool scratch resistance equals 1) and adherent.

EXAMPLE XX Cast ophthalmic lenses made of poly(diethyleneglycol bisallyl)carbonate were coated as in Example XIX with coatings 3.4 micronsthick. The coated lenses were air dried at 35% relative humidity (25C.)for 1 hour, then cured at 140C. for 1 hour. The resulting coatings werehard (steel wool scratch resistance equal to l) and adherent.

EXAMPLE XXI Polymer was prepared according to the following technique.Formaldehyde gas was generated by continuously pyrolyzing cyclohexylhemiformal at approximately 145C. and directing the pyrolysis vapors toa condenser, the temperature of which was regulated to condensecyclohexanol and water and to permit formaldehyde gas to pass through.The vapors then passed through a series of U tubes approximately oneinch in diameter by twelve inches which were filled with stainless steelpacking to remove final traces of impurities. The vapors were directedinto a 500 ml. glass flask equipped with a stirrer, thermocouple, andcontaining 260 parts of benzene, 0.5 part of 2(methyldiethoxysilyl)ethylvinyl ether, and 0.01 part of triphenylmethyl hexafluoroantimonate. Thepolymerization was continued for 20 minutes during which additional .01and .006 part of catalyst and three additional 0.5 part amounts of 2(methyldiethoxysilyl) ethyl vinyl ether were added. The slurry wasstirred with 20 ml. of methanol and 5 ml. of triethylamine, filtered andwashed with three 300-part amounts of methanol and three 300-partamounts of acetone. The washed polymer was dried in a vacuum oven at25C. overnight to yield 17 parts of dry polymer. Incorporation of thesilyl vinyl ether into the formaldehyde chains was evident from the factthat the sample was 38% stable to potassium hydroxide in benzyl alcoholat 165C. (40 minutes) and had a melting point 4C. lower thanhomopolymer.

1 .32 Parts of this polymer were dissolved in 480 parts ofhexafluoroisopropyl alcohol and this solution evaporated onto 88 partsof hand-chopped roving. The fibers were then dried overnight at 55C.under vacuum followed by 1 hour at 110C.

85 Parts of these coated fibers were milled at 190C. for minutes with340 parts of capped polyformaldehyde. The resulting material was choppedand injection molded into test specimens for evaluation.

notched Izod (average of 8) 0.79

range 0.75 to 0.85 Tensile strength (average of 6) 9500 psi.

range 9300 to 9700 psi. Tensile elongation (average of 6) 5.3% range 3.4to 7.0%

1 claim:

1. An article comprising a solid substrate coated with a compositioncomprising 10 to 90 percent by weight of polysilicic acid, measured as$10 and 90 to 10 percent by weight of a silyl-containing compositionconsisting essentially of 100 to about 20 mole percent of at least onesilyl-fluoroolefin polymer made by polymerizing l to 60 mole percent ofa silyl vinyl ether having the formula wherein X is selected from thegroup consisting of an alkylene group containing one to 10 carbon atoms,and an alkyleneoxyalkylene group containing three to 16 carbon atoms, Ris an alkyl group containing one to six carbon atoms, y is 0, l, or 2,and R is an alkyl group containing one to six carbon atoms with 40 to 99mole percent of a substance consisting essentially of 100 to 40 molepercent of at least one polymerizable fluoroolefin of the formula CZ=ZZ" wherein Z is F, Z is F or Cl and Z is H, F, C] W or OW, W beinglower perfluoroalkyl, and 0 to 60 mole percent of a polymerizable vinylether selected from the class consisting of omega-hydroxy alkyl vinylether of three to 13 carbon atoms, alkyl vinyl ether where the alkylportion contains one to 20 carbon atoms, aryl vinyl ether where the arylportion contains six to 20 carbon atoms, aralkyl vinyl ether where thearalkyl portion contains seven to 20 carbon atoms, mono-alkyl,mono-vinyl ethers of mono-alkylene glycols, mono-alkyl, mono-vinylethers of polyalkylene glycols and mixtures thereof; and about 0 to molepercent of a polymer made by polyermizing a substance consistingessentially of 60 to 40 mole percent of at least one polymerizablefluoroolefin of the formula CZ =CZ'Z" wherein Z is F, Z is F or Cl andZ" is H, F, Cl, W or OW, W being lower perfluoroalkyl, and 40 to 60 molepercent of a polymerizable vinyl ether selected from the classconsisting of omegahydroxy alkyl vinyl ether of three to 13 carbonatoms, alkyl vinyl ether where the alkyl portion contains one to 20carbon atoms, aryl vinyl ether where the aryl portion contains six to 20carbon atoms, aralkyl vinyl ether where the aralkyl portion containsseven to 20 carbon atoms, mono-alkyl mono-vinyl ethers of mono-alkyleneglycols, mono-alkyl, mono-vinyl ethers of polyalkylene glycols andmixtures thereof.

2. An article as in claim 1 wherein the coating is 0.5 to 20 micronsthick.

3. An article as in claim 1 in which the solid substrate is atransparent sheet.

4. An article as in claim 3 in which the transparent sheet is acrylicpolymer.

5. An article as in claim 1 in which the solid substrate is polyester.

6. An article as in claim 5 in which the polyester is poly(ethyleneterephthalate).

7. An article as in claim 5 in which the polyester is polycarbonate.

8. An article as in claim 7 in which the polycarbonate ispoly(diphenylol propane )carbonate.

9. An article as in claim 7 in which the polycarbonate ispoly(diethylene glycol bis allyl)carbonate.

10. An article as in claim 1 in the form of a transparent lens.

11. An article as in claim 5 in the form of a transparent ophthalmiclens.

12. An article as in claim 8 in the form of a transparent ophthalmiclens.

13. An article as in claim 9 in the form of a transparent ophthalmiclens.

14. An article as in claim 1 in the form of an ophthalmic lens and inwhich the solid substrate is transparent acrylic polymer.

PQ-ww UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3175 7 Dated February 15, 1974 Matthew Edward Hermes Inventofls) If iscertified that error appears in the above-identified patent and thatsaidLetters Patent are hereby corrected as shown below:

In line 3 of the Abstract; line 47 of column 1; and line 2 of column l6;"change "one" to ---2---.

In line 4 of'rhe- Abstract; line 48 of column 1; and line 3 of column16; change "three" to'-- l---.

Signed Tend sea led this 1mm day of May (SEAL) Attest:

EDWARD M.FLETCI-IER,JR. C. MARSHALLyDANN Attesting; Officer 7Commissioner of Patents

2. An article as in claim 1 wherein the coating is 0.5 to 20 micronsthick.
 3. An article as in claim 1 in which the solid substrate is atransparent sheet.
 4. An article as in claim 3 in which the transparentsheet is acrylic polymer.
 5. An article as in claim 1 in which the solidsubstrate is polyester.
 6. An article as in claim 5 in which thepolyester is poly(ethylene terephthalate).
 7. An article as in claim 5in which the polyester is polycarbonate.
 8. An article as in claim 7 inwhich the polycarbonate is poly(diphenylol propane)carbonate.
 9. Anarticle as in claim 7 in which the polycarbonate is poly(diethyleneglycol bis allyl)carbonate.
 10. An article as in claim 1 in the form ofa transparent lens.
 11. An article as in claim 5 in the form of atransparent ophthalmic lens.
 12. An article as in claim 8 in the form ofa transparent ophthalmic lens.
 13. An article as in claim 9 in the formof a transparent ophthalmic lens.
 14. An article as in claim 1 in theform of an ophthalmic lens and in which the solid substrate istransparent acrylic polymer.